Changes in electronic structure within NiSx (0.60 < x < 1.53) compound series

Abstract

In this article, changes in electronic properties of NiSx series of films with different sulfur content (x = S/Ni) are studied using X-ray (XPS) and ultra-violet (UPS) photoelectron spectroscopy techniques. NiSx (0.60 < x < 1.53) films are synthesized on native oxide of Si(111) substrates via reactive deposition of Ni and S in an ultra-high vacuum chamber by varying the sulfur pressures and substrate temperatures. The binding energy (BE) of Ni2p3/2 core level, the separation between the Ni2p3/2 main peaks and satellite peaks, and the Ni3d valence band binding energies are all found to vary nearly linearly with the sulfur content in NiSx series of compounds, suggesting a direct dependence of Ni electronic charge on the sulfur content. The shift of the Ni3d and S3p states (to higher and lower BE, respectively) with an increase in the S content provides experimental confirmation of the theoretical prediction previously reported (Wen et al., 2020) [1]. All NiSx films showed density of states (DOS) at the Fermi level, indicating their metallic nature. The Ni2p3/2 binding energy shift of NiSx films are much smaller than that of oxide-based compounds, confirming the significantly more covalent nature of the sulfides. NiSx film grown on Si (111) substrate showed nickel silicide interface formation. This study provides information on the growth and trends in the electronic properties of NiSx relevant for their applications in catalysis, energy storage, and electronic devices.